CN101654377A - Surface coating for furnace roller of continuous annealing furnace and after-treatment method thereof - Google Patents
Surface coating for furnace roller of continuous annealing furnace and after-treatment method thereof Download PDFInfo
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- CN101654377A CN101654377A CN200810041983A CN200810041983A CN101654377A CN 101654377 A CN101654377 A CN 101654377A CN 200810041983 A CN200810041983 A CN 200810041983A CN 200810041983 A CN200810041983 A CN 200810041983A CN 101654377 A CN101654377 A CN 101654377A
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Abstract
The invention discloses a surface coating of a furnace roller of a continuous annealing furnace and an after-treatment method thereof. The coating material consists of the following compositions in percentage by weight: 80 to 85 percent of metal mixture CoCrAlY, and 15 to 20 percent of ZrB2 (ceramics), wherein the metal mixture CoCrAlY comprises the following elements in percentage by weight: 70 to 80 percent of Co, 5 to 10 percent of Al, 10 to 20 percent of Cr, and 0.1 to 0.8 percent of Y (sum of Al and Cr is less than or equal to 30 percent). After the furnace roller is sprayed, clearances of the coating are subjected to hole sealing and then the coating is continuously fired at high temperature after hole sealing. The coating and the method improve the clogging resistance of each furnace temperature segment of the annealing furnace. The surface hole sealing treatment eliminates the clearances among spray coatings. A more compact protective film is formed on the coating of the rollersurface after high temperature firing, so the method improves the iron and manganese clogging resistance of the coating.
Description
Technical field
The present invention relates to the coating on metallurgical cold-rolled steel strip continuous annealing unit furnace furnace roller surface, belong to the composition of furnace roller surface spray material especially; Sealing of hole is carried out in the space of spraying back stove roller surface coatings; Sealing of hole carries out high-temperature firing after handling again.
Background technology
It in the cold-rolled steel strip continuous annealing stove nitrogen hydrogen shielding gas; has reductibility; the residual oxide compound of surface of steel plate is reduced into elements such as Fe, Mn under furnace atmosphere; and these elements and furnace roller material (mostly being heat-resistance stainless steel) have very strong affinity, mutual solubility; easily form the buildup that is difficult to remove sticking on the roll surface and with the organism material generation chemical reaction of furnace roller; along with the rising of furnace roller working temperature, the slip between furnace roller and the steel band also promotes the generation of dross in addition.
Influencing the hidden danger of steel band quality in order to eliminate the roll surface buildup. a lot of producers have adopted hot-spraying techniques.The coating that the furnace roller coating technology is exactly the method that adopts thermospray is low in the avidity of furnace roller surface spraying one deck and iron, its thermal expansivity and furnace roller body material are complementary, go back high temperature wear resistant.This coating can prevent that the furnace roller surface from producing buildup, thereby can obtain the good steel plate of surface quality.These coatings should have following properties:
1) resistance to high temperature oxidation: furnace roller also can be worked under the highest operational temperature conditions the long period.
2) anti-thermal shock: the cyclical heat that can stand between normal temperature and the high temperature impacts.
3) resistance to wear: in Working environment, the advantages of good abrasion performance should be arranged.
What traditional furnace roller coating was used is that the coated component system is CoCrAlY-CrB
2/ Y
2O
3, spraying method is supersonic speed or plasma, because these two kinds of spraying method coating void ratios are bigger, the spraying rear surface is also without any processing, uses generally that buildup appears in roll surface after 2～3 months.The buildup major ingredient is Fe, Mn etc., and be difficult to manual removal and remove.In addition, narrate in a lot of documents and in spray material, add CrB
2, CrB
2Really resisting dross has certain help, still, and CrB
2Fusing point lower, generally about 800 ℃, can decompose, and the boron of formation free state, these boron can be attached on the furnace roller surface of back low-temperature zone along with the walking of band steel, when low temperature (450～650 ℃), the manganese of boron and roll surface, iron, etc. combine, and solidify the compound that forms Mn-Fe-B, the roll surface that is attached on that this compound is firm is dross.
Detonation flame spraying also is a kind of emerging spraying method, and representing the spray material trade mark is that (the coated component system is CoCrAlY-10%Al to LCO-17
2O
3), this spraying method coating space is little, and with the bonding strength height of mother metal, but the efficient of detonation flame spraying is lower, general blast frequency is no more than 4-10 time/s, this can cause tangible striped vestige at roll surface, and the furnace roller of this sprayed coating can only be used to produce common cold rolled strip, as the CQ steel grade, to using under the not high situation of surperficial specification of quality, when the detonation flame spraying furnace roller was used for household electrical appliances and automotive sheet production, the striped of roll surface can copy to belt steel surface, can't satisfy the production of high-quality band steel.This defective is called " Pop-Mark ".
Summary of the invention
The technical problem to be solved in the present invention provides a kind of surface coating for furnace roller of continuous annealing furnace and post-treating method thereof, and it can improve the anti-iron of annealing furnace roller, manganese nodulation ability, can eliminate hole between the sprayed coating, can form compact protective film.
For solving the problems of the technologies described above, a kind of surface coating for furnace roller of continuous annealing furnace of the present invention, coated material is by metal mixture and ZrB
2(pottery) formed, and its composition is as follows: (weight percent)
Metal mixture CoCrAlY 80～85%
ZrB
2(pottery) 15～20%
Wherein the metal mixture CoCrAlY weight percent proportioning that accounts for of each element is among Co, Cr, Al, the Y: Co:70～80%, Al:5～10%, Cr:10～20%, Y:0.1～0.8%.
Co has high temperature resistance preferably, and the oxide compound of Y can improve the bonding strength of sprayed coating self, and the oxide compound of Cr can improve oxidation-resistance.The oxide compound of Al not only can improve oxidation-resistance, can also improve the hardness of sprayed coating.
The interpolation of B element can improve resistive connection knurl performance, but general coating is all adopted CrB
2The present invention adds an amount of ZrB
2And do not use traditional CrB
2, mainly based on following reason:
(1) as containing CrB in the coating
2, CrB then
2Hardness is on the low side relatively; What is more important, CrB
2Stability slightly poor, very easy oxygenolysis is Cr
2O
3, and then the facilitation symphysis becomes Mn
1.5Cr
1.5O
4The buildup thing.This kind chemical combination buildup thing not only damages coating performance, and is difficult to manual removal and removes, and causes steel plate defect easily.
(2) CrB
2Fusing point lower, generally about 800 ℃, can decompose, and the boron of formation free state, these boron can be attached on the furnace roller surface of back low-temperature zone along with the walking of band steel, when low temperature (450～650 ℃), the manganese on boron and furnace roller surface, iron, etc. combine, and solidify the compound that forms Mn-Fe-B-O, the roll surface that is attached on that this compound is firm is dross.
(3) the coating chemical stability is analyzed, and whether the chemical stability of material component in the coating is easy to generate the major cause of chemical buildup for coating.Below be ZrB in the coating
2The Theoretical Calculation of antioxidative stabilizer:
4CrB
2+ 3O
2→ 2Cr
2O
3+ 8B (chemical reaction 1)
ΔG＝-1255.337kJ/mol
ZrB
2+ O
2→ ZrO
2+ 2B (chemical reaction 2)
ΔG＝-568.111kJ/mol
According to thermodynamic argument: the value of Δ G is negative more, and then the chemical reaction possibility of carrying out to the right is just big more.Therefore, judge easily: the possibility that chemical reaction 1 takes place is much larger than chemical reaction 2.In other words, ZrB
2Resistance of oxidation be better than CrB
2
But what is more important, a large amount of practice and theoretical analysises all show: Cr
2O
3Be very easy to and Mn element generation chemical reaction, generate Mn
1.5Cr
1.5O
4The buildup thing.
And for ZrB
2Even its oxidation generates ZrO
2, ZrO
2Also be difficult to meeting and Fe, Mn element generation chemical reaction, this also is the anti-Fe of coating, the good major cause of Mn buildup ability.
A kind of post-treating method of surface coating for furnace roller of continuous annealing furnace comprises the steps:
1) after the furnace roller surface spraying hole sealing agent solution is coated in uniformly on the roll surface after the spraying, sealing of hole is carried out in the stove roller surface coatings space;
2) in 500～600 ℃ stove, fired 5～7 hours.
Described post-treating method comprises that also step 3) is increased to 900 ℃～1000 ℃ with furnace temperature after sealing of hole is handled, heated 30～35 hours continuously.
In the described step 1), hole sealing agent is the chromic acid CrO of concentration 5～10%
3Or chromium propylhomoserin (NH
4)
2CrO
4Or heavy chromium propylhomoserin (NH
4)
2Cr
2O
7In the solution any one.
Because the decision of thermospray self technology, the epithelium inside after having sprayed always have a spot of space and exist, such roll surface contacts with belt steel surface, Fe on the band steel, powder such as Mn are easy to embed in the space of sprayed coating, slowly assemble then, formation is difficult to the oxide compound in place to go, causes dross.In order to improve anti-iron, manganese nodulation ability, the present invention adopts on the surface sealing of hole to handle.
Fire under 500～600 ℃ of situations, the sprayed coating surface reaction generates Cr
2O
3, concrete reaction formula is as follows:
CrO
3→ 1/2Cr
2O
3+ 3/4O
2(chemical reaction 3)
(NH
4)
2CrO
4→ 1/2Cr
2O
3+ 2NH
3+ H
2O+3/4O
2(chemical reaction 4)
(NH
4)
2Cr
2O
7→ Cr
2O
3+ 2NH
3+ H
2O+3/2O
2(chemical reaction 5)
Cr
2O
3Thickness be generally: 1～10 μ m, Cr
2O
3Can penetrate in the space of sprayed coating, and Cr
2O
3Particulate can slowly expand under the condition of high temperature, and the space filling of sprayed coating is full.
In order further to improve oxidation-resistance property and hardness, carry out high-temperature firing, promptly after handling, sealing of hole furnace temperature is continued to bring up to 900 ℃～1000 ℃, continuous firing 30～35 hours.CoCrAlY hybrid metal thing can form metal oxide separately when high temperature, following is the balance decomposition pressure of metal oxide in the time of 900 ℃:
Oxidizing reaction balance decomposition pressure (atm)
Co+1/2O
2 
CoO 1.6×10
-12
2Cr+3/2O
2 Cr
2O
3 2.5×10
-22
2Al+3/2O
2 
Al
2O
3 1.3×10
-35
2Y+3/2O
2 
Y
2O
3 1.0×10
-41
As can be seen, the balance decomposition pressure minimum that Y is oxidized forms Y at first from above-listed
2O
3But the ratio of Y has only 0.1～0.8%, and purpose is not to form the anti-oxidation protection film, but because Y
2O
3Can improve the bonding strength of sprayed coating self.
Secondly, Al balance decomposition pressure is also smaller, almost can all form Al
2O
3, Al
2O
3Effect not only can form compact protective film, and guarantee that coating hardness reaches more than the Hv700.Under 900 ℃ condition, Co, Cr are because the balance decomposition pressure is bigger, and the oxide compound of formation seldom.
In high-temperature firing, the Cr that forms on the roll surface when a part of Al and sealing of hole are handled
2O
3React reaction process such as chemical reaction 6:
Cr
2O
3+ 2Al → Al
2O
3+ 2Cr (chemical reaction 6)
The avidity of Al and oxygen is greater than the avidity (Al balance decomposition pressure is less) of Cr and oxygen, and Al is with Cr
2O
3In oxygen seize, form Al
2O
3, the content of Co is also many among the CoCrAlY, but because Co balance decomposition pressure is bigger, can not be with Cr
2O
3In oxygen seize, form the oxide compound of Co.
Handle through above process, the sprayed coating surface is by Al
2O
3All cover Al
2O
3Thickness can reach 30 μ m, Al
2O
3The oxidation-resistance and the hardness of furnace roller surface spray material have been improved.At Al
2O
3The surface is difficult to form the dross thing of metals such as iron, manganese.
The present invention makes it compared with prior art owing to adopted above technical scheme, and have the following advantages and positively effect: this spraying component principal feature is under high-temperature condition, and anti-preferably iron, manganese dross are arranged.From the annealing furnace total system, considered the characteristics of each section furnace temperature, this spraying material not only has resistive connection knurl preferably in high temperature section, and successful solution the dross problem of low-temperature zone.Surface-sealing is handled, and has eliminated the hole between the sprayed coating, has strengthened the anti-iron of coating, manganese dross.On the roll surface sprayed coating, form a kind of more compact protective film behind the high-temperature firing, further improved the anti-iron of coating, manganese dross.
Description of drawings
The present invention is further illustrated with enforcement below with reference to accompanying drawing.
Fig. 1 is surface coating for furnace roller of continuous annealing furnace of the present invention, space sealing of hole and high-temperature firing schematic flow sheet.
Among the figure, the 1st, furnace roller matrix, the 2nd, spraying layered material CoCrAlY-(ZrB
2Pottery), the 3rd, sealing of hole is handled and is generated Cr
2O
3Film, the 4th, high-temperature firing forms Al
2O
3+ a small amount of Cr
2O
3Film.
Embodiment
As shown in Figure 1, be sprayed with coating CoCrAlY-(ZrB on the furnace roller matrix 1
2Pottery) forms coating 2.Embodiment 7-11 (No.1-6 is a comparative example in table 1 and the table 2, and No.7-11 is the embodiment of the invention)
Embodiment 7-11 is the coating composition weight percent proportioning of present embodiment:
Table 1: the composition contrast of embodiment coating and existing coating
Annotate: among the No.1 " other " be Fe content, No.5～11 " other " be inevitable impurity
As shown in Figure 1, the 1st, furnace roller matrix, the 2nd, spraying layered material CoCrAlY-(ZrB
2Pottery), the 3rd, sealing of hole is handled and is generated Cr
2O
3Film, the 4th, high-temperature firing forms Al
2O
3+ a small amount of Cr
2O
3Film.Carry out sealing of hole with hole sealing agent and handle 3 on the space of coating 2 sprayed coatings, after sealing of hole is handled furnace temperature is continued to raise, the coating after handling is realized firing 4, form the anti-oxidation protection film, the sprayed coating surface is by Al
2O
3All cover Al
2O
3Thickness can reach 30 μ m, Al
2O
3The oxidation-resistance and the hardness of furnace roller surface spray material have been improved.At Al
2O
3The surface is difficult to form the dross thing of metals such as iron, manganese.
Table 2: the present embodiment material is through the experiment effect contrast of aftertreatment and current material
Annotate: MN is big more for resistive connection knurl value, and resistive connection knurl performance is good more.
As can be seen from Table 2, comparative example 1,2, the various aspects of performance of 3 detonation flame sprayings still is reasonable, but the main weakness of this spraying method has two:
1, the efficient of detonation flame spraying is lower, and the frequency of generally exploding is no more than 4-10 time/s, and this can cause tangible striped vestige at roll surface, and the striped of roll surface can copy to belt steel surface, can't satisfy the production of high-quality band steel.This defective is called " Pop-Mark ".
2, the Al of detonation flame spraying surface generation
2O
3Be not a lot, the Al that they are a large amount of
2O
3Generate the main roller that relies on when furnace high-temperature uses, slowly separate out.This mode is suitable in high temperature section (850～1000 ℃ of furnace temperature), but can't form Al in low-temperature zone (450～650 ℃ of furnace temperature)
2O
3Protective membrane.Therefore can not use at low-temperature region.
Comparative example 6 as can be seen, void content is than higher, MN is less than embodiment for resistive connection knurl value.
In embodiment 7, the spray material composition is selected table 1 for use, but aftertreatment do not have, the result shows that the resistive connection knurl is poor.
In embodiment 8, the spray material composition is selected table 1 for use, but high-temperature firing has only been carried out in aftertreatment, and the coating voidage is still bigger.
In embodiment 9,10,11, the spray material composition is selected table 1 for use, and sealing of hole and high-temperature firing have been adopted in aftertreatment, and the result shows that the resistive connection knurl is better, and voidage is less.
Actual result: the embodiment of use high low-temperature region in annealing furnace uses continuously the dross phenomenon did not all take place in 2 years, and comparative example uses actual achievement and present embodiment basically identical in high temperature section, but low-temperature region use 3 months less than, just produce serious iron, manganese dross.
Claims (4)
1. surface coating for furnace roller of continuous annealing furnace is characterized in that the weight percent proportioning is:
Metal mixture CoCrAlY:80～85%
ZrB
2：15～20％
Wherein the weight percent proportioning that each element accounts for metal mixture CoCrAlY among Co, Cr, Al, the Y is: Co:70～80%, Al:5～10%, Cr:10～20%, Y:0.1～0.8%.
2. the post-treating method of surface coating for furnace roller of continuous annealing furnace as claimed in claim 1 is characterized in that comprising the steps:
1) after the furnace roller surface spraying hole sealing agent solution is coated in uniformly on the roll surface after the spraying, sealing of hole is carried out in the stove roller surface coatings space;
2) in 500～600 ℃ stove, fired 5～7 hours.
3. the post-treating method of surface coating for furnace roller of continuous annealing furnace as claimed in claim 2 is characterized in that: comprise that also step 3) is increased to 900 ℃～1000 ℃ with furnace temperature after sealing of hole is handled, heated 30～35 hours continuously.
4. as the post-treating method of claim 2 or 3 described surface coating for furnace roller of continuous annealing furnace, it is characterized in that: in the described step 1), hole sealing agent is concentration 5～10% chromic acid CrO
3Or chromium propylhomoserin (NH
4)
2CrO
4Or heavy chromium propylhomoserin (NH
4)
2Cr
2O
7In the solution any one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100419838A CN101654377B (en) | 2008-08-22 | 2008-08-22 | Surface coating for furnace roller of continuous annealing furnace and after-treatment method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100419838A CN101654377B (en) | 2008-08-22 | 2008-08-22 | Surface coating for furnace roller of continuous annealing furnace and after-treatment method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101654377A true CN101654377A (en) | 2010-02-24 |
| CN101654377B CN101654377B (en) | 2012-01-11 |
Family
ID=41708867
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030438A (en) * | 2013-01-04 | 2013-04-10 | 航天材料及工艺研究所 | Glazing agent and preparation method and using method thereof |
| CN110643926A (en) * | 2019-10-25 | 2020-01-03 | 安徽马钢表面技术股份有限公司 | High-temperature furnace roller ZrB of continuous annealing furnace2Modified CoCrAlTaY-Y2O3Protective coating and preparation method thereof |
| CN110965005A (en) * | 2019-11-22 | 2020-04-07 | 江阴市东泰管件有限公司 | High-temperature corrosion resistant coating on surface of heating furnace radiation area collecting pipe and preparation method thereof |
| CN111100972A (en) * | 2020-02-26 | 2020-05-05 | 江苏省沙钢钢铁研究院有限公司 | Method for preventing carbon sleeve roller of continuous annealing furnace from nodulation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2703759A1 (en) * | 2012-09-04 | 2014-03-05 | Schwartz, Eva | Load-bearing medium for ovens |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4519387B2 (en) * | 1999-11-09 | 2010-08-04 | Ｊｆｅスチール株式会社 | Thermal spray coating cermet powder and thermal spray coating roll with excellent build-up resistance |
| CN1904125A (en) * | 2005-07-29 | 2007-01-31 | 上海润馨化学工程技术发展有限公司 | Large power electric arc hot spray coating method of zinc aluminium false alloy |
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2008
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030438A (en) * | 2013-01-04 | 2013-04-10 | 航天材料及工艺研究所 | Glazing agent and preparation method and using method thereof |
| CN103030438B (en) * | 2013-01-04 | 2015-02-11 | 航天材料及工艺研究所 | Glazing agent and preparation method and using method thereof |
| CN110643926A (en) * | 2019-10-25 | 2020-01-03 | 安徽马钢表面技术股份有限公司 | High-temperature furnace roller ZrB of continuous annealing furnace2Modified CoCrAlTaY-Y2O3Protective coating and preparation method thereof |
| CN110965005A (en) * | 2019-11-22 | 2020-04-07 | 江阴市东泰管件有限公司 | High-temperature corrosion resistant coating on surface of heating furnace radiation area collecting pipe and preparation method thereof |
| CN111100972A (en) * | 2020-02-26 | 2020-05-05 | 江苏省沙钢钢铁研究院有限公司 | Method for preventing carbon sleeve roller of continuous annealing furnace from nodulation |
| CN111100972B (en) * | 2020-02-26 | 2021-12-31 | 江苏省沙钢钢铁研究院有限公司 | Method for preventing carbon sleeve roller of continuous annealing furnace from nodulation |
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| Publication number | Publication date |
|---|---|
| CN101654377B (en) | 2012-01-11 |
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